Durable fiber treatment composition

ABSTRACT

A hair treatment composition is presented comprising organomodified silicones having defined physico-chemical properties and an additive which allows the organomodified silicone to be retained on the hair over longer periods of time than traditionally has been the case. The present composition finds particular application on hair that has been damaged through chemical treatments, such as occurs during permanent dyeing, bleaching and permanent waving.

FIELD OF THE INVENTION

[0001] The present invention relates to topical compositions fortreating hair. The topical compositions comprise mixtures offunctionalized silicones having defined physico-chemical properties witha durability additive. The durability additive is capable of modifyingthe functionalized silicones to render them more durable on polarfibrous substrates than previously known silicone based conditioners,especially where the substrate is hair that has been previously damagedthrough chemical treatments, such as occurs during permanent dyeing,bleaching and permanent waving.

BACKGROUND OF THE INVENTION

[0002] Oxidative dyeing, otherwise known as permanent colouring leads toirreversible physico-chemical changes to the hair. Typically, duringthis process, two components are mixed together prior to application tothe hair. These components usually comprise an oxidising agent, such ashydrogen peroxide, and a dyeing material, such as oxidative dyeprecursors and couplers (buffered at a high pH, typically around 10).After contacting with the hair, the mixture is left for a period of timesuitable to allow the required colour transformation to occur, afterwhich the hair becomes more hydrophilic versus non-coloured hair due toirreversible chemical changes. While not wishing to be bound by theory,this change in hair hydrophilicity appears to be due, among otherthings, to the oxidation of the keratin-keratin cysteine amino acidswithin the hair creating more hydrophilic cysteic acid amino acidresidues and the hydrolysis of the hair's natural hydrophobic,protective layer denoted as the F-Layer, a covalently attached lipid tothe outer epicuticular envelope, 18-methyleicosanoic acid. Thiscolouring process is usually repeated regularly by consumers in order tomaintain their desired hair colour and colour intensity and also toensure that new hair growth has the same colour as the older hair. As aconsequence the hair changes polarity from a relatively hydrophobicsurface near the scalp where it could be experiencing its first colour,to a progressively more polar substrate at the hair tips, which may havebeen subjected to multiple colouring treatments. A discussion ofoxidation dyeing of hair can be found in “The Science of Hair Care” byCharles Zviak, Marcel Dekker, New York, 1986. These irreversiblephysicochemical changes can manifest themselves as increased roughness,brittleness and dryness leading to less manageable hair.

[0003] After the colouring process human hair becomes soiled due to itscontact with the surrounding environment and from the sebum secreted bythe scalp. This soiling of the hair causes it to have a dirty feel andunattractive appearance and necessitates shampooing with frequentregularity. Shampooing cleans the hair by removing excess soil andsebum, but can leave the hair in a wet, tangled, and generallyunmanageable state. Once the hair dries, it is often left in a dry,rough, lustreless, or frizzy condition due to the removal of the hair'snatural oils and other natural or deposited conditioning andmoisturizing components. Hair can also be left with increased levels ofstatic upon drying which can interfere with combing and result in acondition commonly referred to as “fly-away-hair”. These conditions tendto be exaggerated on hair which has been previously oxidativelycoloured.

[0004] It is known to use hair conditioners to alleviate the aboveproblems. More specifically, it is known to add conditioning materialsto colorant products or to supply them separately as part of colorantkits. It is also known to use conditioners in the shampooing process.These approaches range from post-shampoo application of hairconditioners such as leave-on or rinse-off products, to hairconditioning shampoos which attempt to both cleanse and condition thehair from a single product. Hair conditioners are typically applied in aseparate step following shampooing. The hair conditioners are eitherrinsed-off or left-on, depending upon the type of product used.Polydimethylsiloxanes (PDMS) are often employed as conditioningmaterials to improve hair feel. However, it is known that, in the caseof more hydrophilic hair obtained after oxidative coloring, PDMSdeposition is greatly reduced, and cannot provide the same benefit inhair condition as for non-oxidatively colored hair. Moreover, PDMS basedconditioners are not retained on the hair for a sufficient period oftime for the benefit to be durable.

[0005] The use of more polar silicones, such as amino-functionalizedsilicones, and even more hydrophilic quat-functionalized silicones isknown—reference is made to EP 0 275 707 and WO 99/49836 on the one handand U.S. Pat. No. 6,136,304 on the other. However, whereas these exhibitimproved deposition onto the more polar damaged hair, their durabilityon such substrates is poor—the increased polarity renders thesesilicones more susceptible to removal via washing (thereby reducingdurability). Without wishing to be bound by theory, this is believed toresult from such silicones having increased aqueous affinity versus theless polar silicones making them more apt to being washed away duringshampooing.

[0006] The addition of organomodified resins to non-polarpolydimethylsiloxanes is known. In WO 92/10161, PDMS-based siliconeconditioners are modified by addition of a resin, in that case toimprove silicone deposition onto undamaged hair. However, this does notaddress the issue of durability onto chemically damaged hair:polydimethylsiloxanes are too non-polar for sufficient deposition ontothe hydrophilic, chemically damaged hair for even an initialconditioning benefit to be achieved, let alone a durable benefit.

[0007] Organomodified siloxane resins have also been added to the veryhydrophilic silicone copolyols. US 2001/0043912 is concerned withtackling the problem of “frizzy” hair and proposes to modify dimethiconecopolyols by addition of a silicone resin to achieve this aim. Thisdocument is not concerned with improving conditioner durability.Moreover, the compositions proposed would not achieve that aim either,since even the resin-modified dimethicone copolyols are far toohydrophilic (100 on the Hydrophilicity Index, detailed below), so wouldbe washed off during any washing step immediately subsequent toapplication.

[0008] With the above discussion in mind, the invention will ideallyprovide a hair treatment composition comprising a conditioning agentthat is durable, i.e. does not wash off so rapidly that the conditioningbenefit is lost to the consumer, especially on chemically damaged hair,such as occurs during permanent dyeing, bleaching and permanent waving.

SUMMARY OF THE INVENTION

[0009] According to a first aspect of the invention, a hair treatmentcomposition is presented, which comprises a mixture of

[0010] (a) a functionalized silicone polymer having an interfacialtension (IFT) of less than or equal to 15 mN/m (15 dyne/cm) and ahydrophilicity index (HI) of 100; and

[0011] (b) a durability additive which is miscible with thefunctionalized silicone

[0012] wherein the mixture has a (Tan δ)⁻¹ greater than zero, and:

[0013] Tan δ=G″/G′

[0014] G′ is the storage modulus

[0015] G″ is the loss modulus

[0016] Wherein said functionalised silicone polymer deposits durably onhair.

[0017] Tan δ describes the ratio of energy lost to energy stored, whereTan δ=G″/G′, G″ is the loss modulus and G′ is the storage modulus. G″and G′ are established by means of the dynamic rheological properties,which, in turn, are measured by an oscillation sweep on a rheometer, asdescribed hereinbelow. More information on the measurement of dynamicrheological properties can be found in “Rheological Properties ofCosmetics and Toiletries” by Dennis Laba, Cosmetic Science andTechnology Series, Volume 13, Marcel Dekker, Inc., ISBN 0-8247-9090-1.

[0018] For the avoidance of doubt, (Tan δ)⁻¹ is directly equivalent to1/(Tan δ).

[0019] The functionalized silicone polymers according to the inventionare capable of depositing durably on hair in all states of damage.

[0020] As used herein, the term “functionalized silicone” includespolydimethylsiloxanes (PDMS) in which at least one methyl group has beenreplaced by a different group, which is preferably not hydrogen; theterm “functionalized silicone” expressly includes the organomodifiedsilicones, as defined hereinbelow. The term “functional silicone” issynonymous with the term “functionalized silicone”.

[0021] The terms “interfacial tension” and “hydrophilicity index” are tobe understood as defined hereinbelow.

[0022] As used herein, the term “durability additive” includes materialswhich improve the durability of the functionalized silicone, as measuredby the Silicone Durability Index Value, as defined hereinbelow. In otherwords, a durability additive is a material which, when mixed with afunctionalized silicone, gives a mixture which is more durable than thefunctionalized silicone alone.

[0023] As used herein, a material Y is “miscible” in a material Z if Yand Z may be mixed to generate a homogenous mixture that does not phaseseparate at standard conditions of temperature and pressure within 3weeks following termination of mixing.

[0024] The term HLB value is known to the skilled person working in thistechnical area—see for example Römpp Chemie Lexikon, Thieme Varlag,Stuttgart, 9^(th) Edition, 1995 under “HLB-Wert”.

DETAILED DESCRIPTION

[0025] All cited references are incorporated herein by reference intheir entireties.

[0026] All percentages given herein are by weight of total compositionunless specifically stated otherwise. All ratios given herein are weightratios unless specifically stated otherwise.

[0027] All molecular weights given herein are weight average molecularweights, unless stated otherwise.

[0028] Except where specific examples of actual measured values arepresented, numerical values referred to herein should be considered tobe qualified by the word “about”.

[0029] In examining how to solve the above technical problems, thepresent inventors moved away from focusing exclusively on molecularproperties and started also to consider what effect altering physicalproperties of silicones might have. That is because we observed thatsilicone droplets tend to interact with strands of hair predominantly asfluids and not as individual molecules. A number of parameters wereinvestigated and matched against the objectives. Functionalizedsilicones tend to exhibit high dynamic mobility, a low melting point (onthe order of −40° C.), a low glass transition temperature (on the orderof −100° C.), and correspondingly fit the Newtonian fluid-model well.Without wishing to be bound by theory, this is probably due to theirreduced steric interactions versus carbon-based chains (absence of sidegroups on O and relatively long Si—O & Si—C bond lengths) leading to aresulting ‘open’ structure, which is responsible for a relatively (toalkanes) low barrier to rotation about the Si—O bond. Being Newtonianfluids, functionalised silicones deform irreversibly, meaning that thefluid does not have a tendency to recover to its original position whenan external force is removed and therefore the energy imparted by theexternal force is fully lost and not stored.

[0030] Surprisingly, the present inventors have found that by bytransforming polar functionalized silicone fluids within a definedhydrophilicity range into moderately viscoelastic fluids with a definedviscoelasticity range, these functionalized silicones can be renderedmore durable in relation to chemically damaged hair, while stillmaintaining the desirable “feel” characteristics of the originalfunctionalized silicones.

[0031] Hydrophilicity has traditionally been measured by means ofinterfacial tension (IFT) which is conventionally established using apendant drop-type method, as defined hereinbelow. The present inventorsalso used such a method as far as they were able. During the course ofour investigations it became apparent, however, that the accuracy of thependant drop method drops off significantly for functionalized siliconeshaving interfacial tensions of less than 1 mN/m (1 dyne/cm). This isbecause the difference in surface energy is so low that the “drop”becomes hard to distinguish from the surrounding medium. Extremelyhydrophilic silicones such as Wetsoft CTW, for example, from WackerSilicones, is so hydrophilic that an IFT measurement using the pendantdrop method is extremely difficult to perform. Unfortunately, thehydrophility region we are interested in includes the region of IFT lessthan 1 mN/m. As a result, the present inventors were forced to adopt analternative method for this region—the so-called hydrophilicity index(HI) as also defined hereinbelow.

[0032] The functionalized silicone fluids of the present invention havean IFT of less than or equal to 15 mN/m and an HI of 100, preferably anIFT of less than 12 mN/m, more preferably an IFT of less than 8 mN/m,more preferably still an IFT of less than 1 mN/m.

[0033] For the sake of completeness, an IFT of 1 mN/m (1 dyne/cm)corresponds to an HI of approximately 85. For ease of comprehension, thelower the IFT value, the higher the corresponding HI value and viceversa.

[0034] The inventors have also uncovered that certain functionalisedsilicones having hydrophilicity index of 100 are capable of depositingdurably on hair in all states of damage. However the precision of thehydrophilicity index method in the region very near to 100 becomesinsufficient to separate useful materials from the materials which aretoo hydrophilic and therefore do not provide the benefits of theinvention. Amongst functionalised silicones having a hydrophilicityindex of 100, the materials which deposit durably and hence useful forthe invention can be identified based on the durability index methoddescribed herein.

[0035] The functionalised silicone fluids of the present inventionpreferably have a Durability Index, as measured by the SiliconeDurability Method protocol, hereinbelow of at least 0.01, preferably atleast 0.1, more preferably at least 0.5, and most preferably at least1.0.

[0036] According to the invention, (tan δ)⁻¹ is greater than zero,preferably from 0.001 to less than or equal to 0.1. Above this upperlimit, the tactile feel performance is reduced, with the mixture offunctionalized silicone/additive becoming sticky and tacky to the touch,reducing acceptance by consumers. More preferably, (tan δ)⁻¹ is from0.01 to less than or equal to 0.075.

[0037] For reference, the following table, Table 1, comprises (Tanδ)⁻¹values of some commercially available polar functional siliconematerials. By mixing such silicones with a durability additive, thevalue of (Tanδ)⁻¹ can be made greater than zero, thereby improving thedurability performance, as demonstrated in Table 2 (see below):Commercial Fluid Supplier (tan □)⁻¹ XS69-B5476 GE Bayer −0.04 KF861 ShinEtsu −0.02 X22-3701E Shin Etsu −0.27 Abilsoft AF100 Goldschmidt −0.15Silwet L8500 OSi Silicones −0.68 Wetsoft CTW Wacker −0.09 DC2-8211 DowCorning −0.19 DC8566 Dow Corning −0.10 Rhodorsil 21637 Rhodia −0.51

[0038] Instrumental values of (Tanδ)⁻¹ which are negative indicate a(Tanδ)⁻¹ value of zero.

[0039] According to an embodiment of the invention, the ratio of theweight of functionalized silicone to durability additive is in the rangefrom 5:1 to 1000:1, preferably from 10:1 to 1000:1 and more preferablyfrom about 20:1 to about 1000:1.

[0040] Hair treatment compositions according to an embodiment of theinvention may comprise from 0.1 to 20%, preferably from 0.50 to 15%,more preferably from 0.50 to 10% and more preferably still from 0.5 to7.5% by weight of the mixture of functionalized silicone fluid anddurability additive.

[0041] Functionalized silicones which may be incorporated intocompositions according to the invention include organomodified siliconesof the pendant or graft type wherein polar functional substituents areincorporated within or onto monovalent organic groups, A¹, A², A³ and A⁴used hereinafter, as follows:

[0042] Also included are the organomodified silicones of the blockcopolymer type wherein these polar functional substituents areincorporated within or onto bivalent organic groups, A¹, A², A³ and A⁴used hereinafter.

[0043] where Me is methyl, m is greater than or equal to 1, n is about50 to 2000, p is about 0 to 50, q is about 0 to 50, r is about 0 to 50,s is about 0 to 50, wherein p+q+r+s is greater than or equal to 1, B¹ isH, OH, an alkyl or an alkoxy group.

[0044] The above functionalized silicones of the pendant or blockcopolymer type can also incorporate silicone branching groups includingMeSiO_(3/2), known as silsesquioxane or T groups, and SiO_(4/2), knownas Q groups by those skilled in the art.

[0045] Organic groups A¹, A², A³ and A⁴ may be straight, branched ormono- or polycyclic aliphatic, mono or polyunsaturated alkyl, aryl,heteroalkyl, heteroaliphatic or heteroolefinic moiety comprising 3 to150 carbon atoms together with 0-50 heteroatoms, especially 0, N, S, Pand can incorporate one or more polar substituents selected fromelectron withdrawing, electron neutral, or electron donating groups withHammett sigma para values between −1.0 and +1.5 which can be non-ionic,zwitterionic, cationic or anionic comprising, for example, groups α¹,α², α³, and α₄ as defined below; S-linked groups including Sα¹, SCN,SO₂α¹, SO₃α¹, SSα1¹, SOα¹, SO₂Nα¹α², SNα₁α², S(Nα¹) α², S(O)(Nα¹) α²,Sα¹(Nα²), SONα¹α²; O-linked groups including Oα¹, OOα¹, OCN, ONα¹α²;N-linked groups including Nα¹α², Nα¹α²α³+, NC, Nα¹Oα², Nα¹Sα², NCO, NCS,NO₂, N=Nα¹, N=NOα¹, Nα¹CN, N=C=Nα¹, Nα¹Nα²α³, Nα¹Nα²Nα³α⁴, Nα¹N=Nα²;other miscellaneous groups including COX, CON₃, CONα¹α², CONα¹COα²,C(=Nα¹)Nα¹α², CHO, CHS, CN, NC, and X.

[0046] α¹, α², α³, and α⁴ may be straight, branched or mono- orpolycyclic aliphatic, mono or polyunsaturated alkyl, aryl, heteroalkyl,heteroaliphatic or heteroolefinic moiety comprising 3 to 150 carbonatoms together with 0-50 heteroatoms, especially 0, N, S, P.

[0047] X is F, Cl, Br, or I.

[0048] H is hydrogen, O is oxygen, N is nitrogen, C is carbon, S issulfur, Cl is chlorine, Br is bromine, I is iodine, F is fluorine.

[0049] Hammett sigma para values are discussed in Römpp Chemie Lexikon,Georg Thieme Verlag, Stuttgart, New York, 9^(th) Edition, 1995 under“Hammett Gleichung”.

[0050] Preferred polar functional substituents for use in the presentinvention as described include, but are not limited to, polyoxyalkylene(polyether), primary and secondary amine, amide, quaternary ammonium,carboxyl, sulfonate, sulfate, carbohydrate, phosphate, and hydroxyl.More preferably, the polar functional substituents of the presentinvention include, but are not limited to polyoxyalkylene, primary andsecondary amine, amide and carboxyl.

[0051] Suitable functionalized silicones according to the presentinvention include, but are not limited to, organomodified silicones withamine functionality available commercially under the trade names such asADM1100 and ADM1600 from Wacker Silicones, DC2-8211, DC8822, DC8822A,DC8803, DC2-8040, DC2-8813, DC2-8630 and DC8566 from Dow CorningCorporation, KF-862, KF-861, KF-862S, KF-8005, KF-8004, KF-867S, KF-873,and X-52-2328 from Shin-Etsu Corporation, and TSF 4702, TSF 4703, TSF4704, TSF 4705, TSF 4707, TSF 4708, TSF 4709, F42-B3115, SF 1708, SF1923, SF 1921, SF 1925, OF TP AC3309, OF 7747, OF-NH TP Al3631, OF-NH TPAl3683 from GE Bayer Silicones and organomodified siliciones with amineand polyether functionality available commercially under the trade namessuch as XS69-B5476 from GE Bayer Silicones and Abilsoft AF100 fromGoldschmidt.

[0052] Preferred polar functional substituents for inclusion within thefunctionalized silicone contain at least one class of oxygen containingpolar functional substituent, such that the oxygen content (% oxygen)within the summation of the one or more polar functional substituents(not including the oxygen in the PDMS backbone) is from 1% to 17%,preferably from 2% to 15%, and more preferably from 3% to 13% of theweight of the functionalized silicone. In addition, the hydrophilicfunctional silicone components of the present invention should have asilicone content (% silicone) of from 45 to 95%, preferably from 50 to90%, and more preferably from 55 to 85% of the weight of thefunctionalized silicone. The silicone content or calculated percentsilicone (% silicone) is defined as the average molecular weight of thePDMS backbone (consisting of silicon, oxygen and any directly attachedmethyl groups) divided by the average molecular weight of the wholepolymer. Similarly, the overall oxygen content (% oxygen) is defined asthe molecular weight of each oxygen atom multiplied by the averagenumber of oxygen atoms present on the silicone and then divided by theaverage molecular weight of the whole polymer.

[0053] More preferably, the functionalized silicone polymer comprisespolyoxyalkylene substituents. The polyoxyalkylene content (% polyether)should be from 5 to 55%, preferably from 10 to 50%, and more preferablyfrom 15 to 45%. Preferably, the sum of % silicone and % polyether doesnot total 100%, other constituents, such as amine and amide making upthe balance. The silicone content is defined above and the polyethercontent (% polyether) is defined as the molecular weight of eachpolyether pendant or block multiplied by the average number of pendantsor blocks and divided by the average molecular weight of the wholepolymer. If the pendant or block polyether comprises of both ethyleneoxide (EO) and propylene oxide (PO) units, then this % polyethercomprises the summation of % EO and % PO. If the pendant or blockpolyether is comprised of either only EO or only PO units, this %polyether is equivalent to the %EO or %PO, respectively.

[0054] More preferably still, the functionalized silicone is accordingto the following formula (1):

[0055] where Me equals methyl; R¹ is methyl or R² or R³; R² is—(CH₂)_(a)—NH—[(CH₂)_(a)—NH]_(b—H;)

[0056] and R³ is —(CH₂)_(a)—(OC₂H₄)_(m)—(OC₃H₆)_(n)—OZ; wherein x isabout 50 to 1500, y is about 1 to 20, z is about 1 to 20; a is about 2to 5, preferably 2 to 4; b is 0 to 3, preferably 1; m is about 1 to 30;n is about 1 to 30, and Z is H, an alkyl group with 1-4 carbons, or anacetyl group, with the proviso that when y is 0, R¹ is an R² group, andwhen z is 0, R¹ is an R³ group.

[0057] The pendant organomodified silicones comprising amino andpolyoxyalkylene groups of the average formula (1) can be prepared bymethods known to those skilled in the art, via steps including knownpolymerisation reactions (e.g. equilibration or polycondensation) andknown methods of introducing organic substitution to the siliconebackbone (e.g. hydrosililation).

[0058] The following are non-limiting exemplary structures of thefunctionalized silicone according to the present invention.

[0059] Material A

[0060] In Example A, molecular weight=18738; % oxygen=5.21% (contributedby thirty one oxygen atoms); and % silicone = 81.42% % polyether =16.33% % other* =  2.25% 100.00% 

[0061] *contributed by other side chain and the —(CH₂)₃— and —OHmoieties on the polyether side chain.

[0062] Preferably, the durability additive according to the inventioncomprises one or more organosiloxane resins.

[0063] Without wishing to be bound by theory, organosiloxane resins arebelieved to create a 3-dimensional network within the functionalizedsilicone fluid giving rise to vicoelasticity thereby improving theadhesive properties of the fluid and hence the durability on a fibroussubstrate. Preferably, the organosiloxane resin is insoluble in water.In the case that the fiber treatment composition is an emulsion, themixture of the functionalized silicone and the organosiloxane resin maybe dispersed therewithin in the form of emulsified droplets.

[0064] Organosiloxane resins which my be included in the durabilityadditive according to the invention comprise combinations of R₃SiO_(1/2)“M” units, R₂SiO “D” units, RsiO_(3/2) “T” units, SiO₂ “Q” units inratios to each other that satisfy the relationship R_(n)SiO_((4-n)/2)where n is a value between 1.0 and 1.50 and R is a methyl group. Silanolor alkoxy functionalities may also be present in the resin structure.

[0065] More preferably, the organosiloxane resins comprise repeatingmonofunctional R₃SiO_(1/2) “M” units and the quadrafunctional SiO₂ “Q”units, otherwise known as “MQ” resins. In this case, the ratio of the“M” to “Q” functional units is advantageously from 0.7 and the value ofn is 1.2. Organosiloxane resins such as these are commercially availableas SR1000 available from GE Bayer Silicones and Wacker 803 from WackerSilicones.

[0066] Advantageously, the organosiloxane resins according to theinvention are solid at about 25° C. and have a molecular weight range offrom 1,000 to 10,000 grams/mole.

[0067] Reference is made to Table 2, which demonstrates the improvementin durability that may be achieved by adding MQ resin to somecommercially available functionalized silicones: TABLE 2 Durability onchemically Silicone damaged hair (%) Silicone Z¹  0 Silicone Z¹ + 1% MQresin²  0 Silicone Z¹ + 5% MQ resin² 19 Silicone Z¹ + 10% MQ resin² 24XS69-B5476⁴  7 XS69-B5476⁴ + 0.5% MQ resin²  9 XS69-B5476⁴ + 1% MQresin² 13 XS69-B5476⁴ + 2% MQ resin² 19 XS69-B5476⁴ + 10% MQ resin² 19DC-2-8566³ 11 DC-2-8566³ + 0.05% MQ resin² 52 Rhodorsil 21637⁵  2Rhodorsil 21637⁵ + 0.5% MQ resin² 52 Rhodorsil 21637⁵ + 1.0% MQ resin²100 

[0068] The hair treatment composition according to the invention mayadditionally comprise a hair bleaching component and/or a hair dyeingcomponent.

[0069] According to a further aspect of the invention, a hair treatmentkit is provided comprising:

[0070] (a) an oxidative bleaching composition

[0071] (b) a dye composition

[0072] a hair treatment composition as defined hereinabove comprisedwithin component (a) and/or within component (b) and/or provided as aseparate component.

[0073] The hair treatment composition according to the present inventionmay include a cosmetically acceptable vehicle to act as a diluent,dispersant, or carrier for the silicone oil in the composition, so as tofacilitate the distribution of the silicone oil when the composition isapplied. The vehicle may be an aqueous emulsion, water, liquid or solidemollients, solvents, humectants, propellants, thickeners and powders.

[0074] Advantageously, the hair treatment compositions according to thepresent invention may be in the form an emulsion with water as a primarycomponent, although aqueous organic solvents, may also be included. Theemulsion may be a water-in-oil emulsion, an oil-in-water emulsion, awater-in-oil-in-water multiple emulsion, or an oil-in-water-in-oilmultiple emulsion, but is preferably an oil-in-water emulsion (asilicone-in-water emulsion).

[0075] The aqueous continuous phase of the emulsion treatmentcompositions of the present invention may further comprise an emulsifierto facilitate the formation of the emulsion. Emulsifiers for use in theaqueous continuous phase of the present emulsion treatment compositionsmay include an anionic surfactant, cationic surfactant, amphotericsurfactant, water-soluble polymeric surfactant, water-solublesilicone-containing surfactant, nonionic surfactant having an HLB ofgreater than about 10, or a surfactant system capable of formingstabilizing liquid crystals around the silicone droplets. The nonionicsurfactant preferably has an HLB of at least 12, and more preferably, anHLB value of at least about 15. Surfactants belonging to these classesare listed in McCutcheon's Emulsifiers and Detergents, North Americanand International Editions, MC Publishing Co., Glen Rock N.J., pages235-246 (1993).

[0076] The emulsifier for the aqueous phase does not gel the aqueousphase. The emulsifier may, however, be capable of forming a stabilizinglayer of lamellar liquid crystals around silicone droplets. This barrierfilm prevents coalescence between emulsion droplets. In this case, thesurfactant system may be a single surfactant or a blend of surfactants.In some cases, a particular surfactant cannot form a liquid crystalstructure alone, but can participate in the formation of liquid crystalsin the presence of a second surfactant. Such a surfactant system forms alayer of lamellar liquid crystals around the silicone to provide abarrier between the silicone and the aqueous phase. This type of anemulsion is different from the conventional emulsions, which rely uponthe orientation of the hydrophobic and hydrophilic components of asurfactant at an silicone-water interface. The formation of a layer oflamellar liquid crystals around the silicone can be detected by thepresence of Maltese crosses viewed by optical microscopy through crossedpolarizing plates or by freeze fracture electron microscopy.

[0077] Exemplary classes of surfactants capable of participating in theformation of a liquid crystal structure around the silicone dropletsinclude, but are not limited to specific cationic surfactants, anionicsurfactants, nonionic surfactants, quaternary ammonium surfactants andlipid surfactants.

[0078] Specific nonionic surfactants are fatty alcohols or fatty acids,or derivatives thereof, or a mixture of any of these, having a chainlength of from about 14 to about 20 carbon atoms. These materials may bepredominantly linear or may be branched. Some examples include myristylalcohol, myristic acid, cetyl alcohol, palmitic acid, cestearyl alcohol,stearyl alcohol, stearic acid, oleic acid, oleyl alcohol, arachidylalcohol, arachidic acid, and mixtures thereof.

[0079] Other specific non-ionic surfactants include condensationproducts of aliphatic (C₁₆ to C₂₂) primary or secondary linear orbranched chain alcohols or phenols with alkylene oxides, usuallyethylene oxide, and generally having from 1 to 30 ethylene oxide groups.Some examples include, but are not limited to, ceteth-1, ceteth-2,ceteth-3, ceteth-4, ceteth-5, ceteth-6, ceteth-10, ceteth-12, ceteth-14,ceteth-15, ceteth-16, ceteth-20, ceteth-24, ceteth-25, ceteth-30,ceteareth-2, ceteareth-3, ceteareth-4, ceteareth-5, ceteareth-6,ceteareth-7, ceteareth-8, ceteareth-9, ceteareth-10, ceteareth-11,ceteareth-12, ceteareth-13, ceteareth-14, ceteareth-15, ceteareth-16,ceteareth-17, ceteareth-18, ceteareth-20, ceteareth-22, ceteareth-23,ceteareth-24, ceteareth-25, ceteareth-27, ceteareth-28, ceteareth-29,ceteareth-30, steareth-2, steareth-3, steareth-4, steareth-5,steareth-6, steareth-7, steareth-8, steareth-10, steareth-11,steareth-13, steareth-14, steareth-15, steareth-16, steareth-20,steareth-21, steareth-25, steareth-27, steareth-30, arachideth-20,beheneth-5, beheneth-10, beheneth-20, beheneth-25, beheneth-30 andmixtures thereof.

[0080] Specific cationic surfactants include quaternary ammoniumhalides, e.g., alkyltrimethylammonium halides in which the alkyl grouphas from about 12 to 22 carbon atoms, for exampledodecyltrimethyl-ammonium chloride, hexadecyltrimethylammonium chloride,cetyltrimethylammonium chloride, behenyltrimethylammonium chloride,benzyltrimethylammonium chloride, octyldimethylbenzyl-ammonium chloride,decetyldimethylbenzylammonium chloride, stearyldimethylbenzylammoniumchloride, distearyldimethylammonium chloride, didodecyldimethylammoniumchloride, dioctadecyidimethylammonium chloride, tallow trimethylammoniumchloride, cocotrimethyl-ammonium chloride, cetylpyridinium chloride andtheir other corresponding halide salts and hydroxides. Preferredcationic surfactants are cetyltrimethylammonium chloride (CTAC) andcetyltrimethylammonium bromide (CTAB 99% from Fluka, CTAC 50% (Arquad16-50, Akzo). Preferably, cationic surfactants are used at 2-10% withCTAC and CTAB being the preferred cationic surfactants. Additionally,when mono-alkyl substituted cationic surfactants are used, it ispreferred to also employ cholesterol wherein the ratio of cholesterol tocationic surfactant ranges from 0.1:1.0 to 1.0:1.0, more preferably from0.5:1.0 to 1.5:1.0, and most preferably 0.7:1.0 to 1.25:1.0.

[0081] Specific anionic surfactants are di-alkyl sulfonates, di-alkylether sulfonates, di-alkylaryl sulfonates, di-alkanoyl isethionates,di-alkyl succinates, di-alkyl sulfosuccinates, di-N-alkoyl sarcosinates,di-alkyl phosphates, di-alkyl ether phosphates, di-alkyl ethercarboxylates, and di-alpha-olefin sulfonates, especially their sodium,magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyland acyl groups generally contain from 12 to 20 carbon atoms and may beunsaturated.

[0082] The stabilizing liquid crystals may also be formed from lipidsurfactants including either phospholipids, i.e., based on glycerol andsphingosine, or glycolipid, i.e. based on sphingosine. Phospholipids arepreferred with phosphatidyl choline (lecithin) being the preferredphospholipid. Of the alcohol moieties which comprise thephosphoglycerides, serine, choline and ethanolamine are particularlypreferred, and of the fatty chains, those having a chain length of C₁₄to C₂₄ are preferred. The fatty acid chains may be branched orunbranched, saturated or unsaturated, and palmitic, myristic, oleic,stearic, arachidonic, linolenic, linoleic and arachidic acids areparticularly preferred.

[0083] Preferred surfactants for the formation of liquid crystals in theaqueous continuous phase are of the nonionic type and include C₁₆₋₂₂fatty alcohols, and C₁₆₋₂₂ fatty alcohol ethoxylates with 1 to 30ethylene oxide groups. Specific examples include cetearyl alcohol, cetylalcohol, stearyl alcohol, arachidyl alcohol, oleyl alcohol, cetearethethoxylates with between 10 and 30 ethylene oxide groups, cetethethoxylates with between 10 to 30 ethylene oxide groups, stearethethoxylates with between 10 and 30 ethoxylates, and combinationsthereof. Preferably, C₁₆₋₂₂ fatty alcohols are used in combination withC₁₆₋₂₂ fatty alchol ethoxylates at a ratio of between 10:1 to 0.5:1,more preferably between 6:1 and 1:1, and most preferably between 5:1 and1.5:1.

[0084] The aqueous continuous phase should ideally comprise theemulsifier in an amount sufficient to stabilize the silicone. In oneembodiment, the aqueous continuous phase comprises the emulsifier in anamount of from about 0.1% to about 15%, and more preferably from about0.1% to about 10%, based on the weight of the aqueous continuous phase.

[0085] The composition according to the present application findsparticular utility in hair coloring compositions especially oxidativehair colorants wherein the hair is subjected to a particularlyaggressive environment.

[0086] A preferred hair coloring agent for use herein is an oxidativehair coloring agent. The concentration of each oxidative hair coloringagent in the compositions according to the present invention may be fromabout 0.0001% to about 5% by weight.

[0087] Any oxidative hair coloring agent can be used in the compositionsherein. Typically, oxidative hair coloring agents comprise at least twocomponents, which are collectively referred to as dye formingintermediates (or precursors). Dye forming intermediates can react inthe presence of a suitable oxidant to form a colored molecule.

[0088] The dye forming intermediates used in oxidative hair colorantsinclude: aromatic diamines, aminophenols, various heterocycles, phenols,napthols and their various derivatives. These dye forming intermediatescan be broadly classified as; primary intermediates and secondaryintermediates. Primary intermediates, which are also known as oxidativedye precursors, are chemical compounds which become activated uponoxidation and can then react with each other and/or with couplers toform colored dye complexes. The secondary intermediates, also known ascolor modifiers or couplers, are generally colorless molecules which canform colors in the presence of activated precursors/primaryintermediates, and are used with other intermediates to generatespecific color effects or to stabilise the color.

[0089] Primary intermediates suitable for use in the compositions andprocesses herein include: aromatic diamines, polyhydric phenols, aminophenols and derivatives of these aromatic compounds (e.g., N-substitutedderivatives of the amines, and ethers of the phenols). Such primaryintermediates are generally colorless molecules prior to oxidation.

[0090] While not wishing to be bound by any particular theory, it isbelieved that the process by which color is generated from these primaryintermediates and secondary coupler compounds generally includes astepwise sequence whereby the primary intermediate can become activated(by oxidation), and then enjoins with a coupler to give a dimeric,conjugated colored species, which in turn can enjoin with another‘activated’ primary intermediate to produce a trimeric conjugatedcolored molecule.

[0091] In general terms, oxidative dye primary intermediates includethose materials which, on oxidation, form oligomers or polymers havingextended conjugated systems of electrons in their molecular structure.Because of the new electronic structure, the resultant oligomers andpolymers exhibit a shift in their electronic spectra to the visiblerange and appear colored. For example, oxidative primary intermediatescapable of forming colored polymers include materials such as aniline,which has a single functional group and which, on oxidation, forms aseries of conjugated imines and quinoid dimers, trimers, etc. ranging incolor from green to black. Compounds such as p-phenylenediamine, whichhas two functional groups, are capable of oxidative polymerization toyield higher molecular weight colored materials having extendedconjugated electron systems. Oxidative dyes known in the art can be usedin the compositions according to the present invention. A representativelist of primary intermediates and secondary couplers suitable for useherein is found in Sagarin, “Cosmetic Science andTechnology”,”Interscience, Special Ed. Vol. 2 pages 308 to 310.

[0092] The primary intermediates can be used alone or in combinationwith other primary intermediates, and one or more can be used incombination with one or more couplers. The choice of primaryintermediates and couplers will be determined by the color, shade andintensity of coloration which is desired. There are nineteen preferredprimary intermediates and couplers which can be used herein, singly orin combination, to provide dyes having a variety of shades ranging fromash blonde to black; these are: pyrogallol, resorcinol,p-toluenediamine, p-phenylenediamine, o-phenylenediamine,m-phenylenediamine, o-aminophenol, p-aminophenol, 4-amino-2-nitrophenol,nitro-p-phenylenediamine, N-phenyl-p-phenylenediamine, m-aminophenol,2-amino-3-hydroxypyridine, 1-napthol, N,N bis(2-hydroxyethyl)p-phenylenediamine, resourcinol, diaminopyrazole,4-amino-2-hydroxytoluene, 1,5-dihydroxynapthalene, 2-methyl resorcinoland 2,4-diaminoanisole. These can be used in the molecular form or inthe form of peroxide-compatible salts.

[0093] The hair coloring compositions of the present invention may, inaddition to or instead of an oxidative hair coloring agent, includenon-oxidative and other dye materials. Optional non-oxidative and otherdyes suitable for use in the hair coloring compositions and processesaccording to the present invention include both semi-permanent,temporary and other dyes. Non-oxidative dyes as defined herein includethe so-called ‘direct action dyes’, metallic dyes, metal chelate dyes,fiber reactive dyes and other synthetic and natural dyes. Various typesof non-oxidative dyes are detailed in: ‘Chemical and Physical Behaviourof Human Hair’ 3rd Ed. by Clarence Robbins (pp250-259); ‘The Chemistryand Manufacture of Cosmetics’. Volume IV. 2nd Ed. Maison G. De Navarreat chapter 45 by G. S. Kass (pp841-920); ‘cosmetics: Science andTechnology’ 2nd Ed., Vol. 11 Balsam Sagarin, Chapter 23 by F. E. Wall(pp 279-343); ‘The Science of Hair Care’ edited by C. Zviak, Chapter 7(pp 235-261) and .‘Hair Dyes’, J.C. Johnson, Noyes Data Corp., ParkRidge, U.S.A. (1973), (pp 3-91 and 113-139).

[0094] The hair coloring compositions herein preferably comprise atleast one oxidising agent, which may be an inorganic or organicoxidising agent. The oxidising agent is preferably present in thecoloring composition at a level of from about 0.01% to about 10%,preferably from about 0.01% to about 6%, more preferably from about 1%to about 4% by weight of the composition.

[0095] A preferred oxidising agent for use herein is an inorganicperoxygen oxidising agent. The inorganic peroxygen oxidising agentshould be safe and effective for use in the present compositions.Preferably, the inorganic peroxygen oxidising agents suitable for useherein will be soluble in the compositions according to the presentinvention when in liquid form or in the form intended to be used.Preferably, inorganic peroxygen oxidising agents suitable for use hereinwill be water-soluble. Water soluble oxidising agents as defined hereinmeans agents which have a solubility to the extent of about log in 1000ml of deionised water at 25° C. (“Chemistry” C. E. Mortimer. 5th Edn.p277).

[0096] The inorganic peroxygen oxidising agents useful herein aregenerally inorganic peroxygen materials capable of yielding peroxide inan aqueous solution. Inorganic peroxygen oxidising agents are well knownin the art and include hydrogen peroxide, inorganic alkali metalperoxides such as sodium periodate, sodium perbromate and sodiumperoxide, and inorganic perhydrate salt oxidising compounds, such as thealkali metal salts of perborates, percarbonates, perphosphates,persilicates, persulphates and the like. These inorganic perhydratesalts may be incorporated as monohydrates, tetrahydrates etc. Mixturesof two or more of such inorganic peroxygen oxidising agents can be usedif desired. While alkali metal bromates and iodates are suitable for useherein the bromates are preferred. Highly preferred for use in thecompositions according to the present invention is hydrogen peroxide.

[0097] The compositions herein may instead or in addition to theinorganic peroxygen oxidising agent(s), comprise one or more preformedorganic peroxyacid oxidising agents.

[0098] Suitable organic peroxyacid oxidising agents for use in thecoloring compositions according to the present invention have thegeneral formula:

R—C (O) OOH

[0099] wherein R is selected from saturated or unsaturated, substitutedor unsubstituted, straight or branched chain, alkyl, aryl or alkarylgroups with from 1 to 14 carbon atoms.

[0100] The organic peroxyacid oxidising agents should be safe andeffective for use in the compositions herein. Preferably, the preformedorganic peroxyacid oxidising agents suitable for use herein will besoluble in the compositions used according to the present invention whenin liquid form and in the form intended to be used. Preferably, organicperoxyacid oxidising agents suitable for use herein will bewater-soluble. Water-soluble preformed organic peroxyacid oxidisingagents as defined herein means agents which have a solubility to theextent of about 10 g in 1000 ml of deionised water at 25° C.(“Chemistry” C. E. Mortimer. 5th Edn. p277).

[0101] The compositions herein may optionally contain a transition metalcontaining catalyst for the inorganic peroxygen oxidising agents and theoptional preformed peroxy acid oxidising agent(s). Suitable catalystsfor use herein are disclosed in WO98/27945.

[0102] The compositions herein may contain as an optional component aheavy metal ion sequestrant. By heavy metal ion sequestrant it is meantherein components which act to sequester (chelate or scavenge) heavymetal ions. These components may also have calcium and magnesiumchelation capacity, but preferably they show selectivity to bindingheavy metal ions such as iron, manganese and copper. Such sequesteringagents are valuable in hair coloring compositions as herein describedfor the delivery of controlled oxidising action as well as for theprovision of good storage stability of the hair coloring products.

[0103] Heavy metal ion sequestrants may be present at a level of fromabout 0.005% to about 20%, preferably from about 0.01% to about 10%,more preferably from about 0.05% to about 2% by weight of thecompositions.

[0104] Suitable sequestering agents are disclosed in WO98/27945.

[0105] For use, the treatment compositions according to an embodiment ofthe invention may be provided at a pH from about 3 to 11, preferablyfrom 4 to 10.5.

[0106] Test Methods

[0107] Hydrophilicity Index Method:

[0108] The hydrophilicity indexes were measured via turbidimetry on anLP2000 Turbidity Meter from Hanna Instruments, Bedfordshire, UnitedKingdom.

[0109] A 100 ml beaker is thoroughly cleaned, including prior rinsingwith hexane then ethanol, and then dried:

[0110] 1. 0.3500 grams (+/− 0.0015 g) of the functionlized silicone isweighed directly into the beaker.

[0111] 2. 24.6500 grams (+/− 0.0500 g) of ethanol (ethyl alcohol, 99.7%vol/vol minimum, A.R. quality, EEC No. 200-578-6) is then weigheddirectly into the beaker.

[0112] 3. The contents of the beaker is then mixed thoroughly via a highshear mixer (IKA Labortechnik-Ultra-Turrax T8 from IKA Werke GmbH & Co.KG, Staufen,

[0113] Germany) for 1 minute with special attention to ensure thesilicone is completely removed from the bottom of the beaker and therebymixed properly.

[0114] 4. Immediately dispense using a pipette, 10 ml of the resultingliquid into a clean cuvette (Note: The cuvette is thoroughly rinsed withhexane twice, then rinsed with ethanol twice and then dried prior toreadings) which is then loaded into the turbidity meter.

[0115] 5. After approximately 30 seconds a turbidity reading isrecorded, immediately followed by a second reading for verification.

[0116] 6. Steps 1-5 are repeated 3 times, the turbidity values beingaveraged to give the average turbidity reading for the functionalizedsilicone.

[0117] The hydrophilicity index for the functionalized silicone is thencomputed as follows:

Hydrophilicity Index=100−((Average turbidity)/400)×100

[0118] Interfacial Tension Measurement Protocol

[0119] The silicone/water interfacial tensions of the organomodifiedsilicones were measured via pendant drop shape analysis on a KrussDSA-10 instrument as taught in F. K. Hansen, G. Rodsrun, “Surfacetension by pendant drop. A fast standard instrument using computer imageanalysis”, Journal of Colloid and Interface Science, Volume 141, Issue1, January 1991, pages 1-9. The accuracy of this method is dependentupon the density difference between the reference fluid (usually water)and the test fluid. Given that many of the present functionalizedsilicones have densities approaching that of water, D₂O (with a densityof 1.1 g/cm⁻³) was substituted for H₂O as the more dense phase, in orderto ensure a sufficient density difference. The respective densities ofthe organomodified silicones were measured with a Calculating PrecisionDensity Meter DMA 55 instrument from Apollo Scientific Limited.

[0120] Viscosity of Functionalized Silicone Fluids—Measurement Protocol

[0121] An AR 500 rotational rheometer (TA Instruments Ltd., Leatherhead,Surrey KT22 7UQ, UK) is used to determine the viscosity of thefunctionalized silicone fluids used herein. The determination isperformed at 30° C., with the 4 cm 2° steel cone measuring system setwith a 49 μm (micron) gap and is performed via the programmedapplication of a shear stress of 0.5 to 590 Pa over a 2 minute timeperiod. These data are used to create a shear rate vs. shear stresscurve for the material. This flow curve can then be modelled in order toprovide a material's viscosity. These results were fitted with thefollowing well-accepted Newtonian model:

Viscosity, μ=σ/γ

(where σ is shear stress; γ is shear rate)

Silicone Durability Method

[0122] Hair Substrate Preparation Method

[0123] Durability is only assessed on a polar, chemically damaged hairsubstrate. Hair is supplied by Hugo Royer International Limited (10Lakeside Business Park, Sandhurst, Berkshire, GU47 9DN, England) and isa blended, Eastern European, mid-brown human hair. Prior to use, thehair is assessed and qualified for low cuticular damage (<20%) andmisalignment (<5%), based on at least 200 hair strands per batch. Anydamage on a hair strand counts as one point damaged, and then the totalis calculated as a percentage. This hair is made into 4″ (10 cm), 2 ground tied switches (where the length and weight of hair corresponds tothe hair below the tie).

[0124] Hair switches are chemically damaged using the following twocomponent bleaching formulations: Peroxide base Ingredients Wt/Wt % 1.Emulsion base: Deionized water 29.78 Cetyl alcohol (1) 2.24 Stearylalcohol (2) 2.24 Ceteareth-25 (3) 1.50 Phenoxyethanol (4) 0.11 Sodiumbenzoate (5) 0.09 Tetrasodium EDTA (87%) (6) 0.04 2. Chelant premixDeionized water 35.72 Pentasodium pentetate (40%) (7) 0.24 Hydroxyethanediphosphonic acid (60%) 0.16 (8) Phosphoric acid (75%) (9) 0.08 Sodiumstannate (95%) (10) 0.04 3. Peroxide mix Hydrogen peroxide (35%) (11)17.15 Deionized water 10.61

[0125] Carrier base for dye base Ingredients Wt/Wt % 1. Acetic acidpre-mix Deionized water 46.49 Acetic acid (50%) (12) 3.91 2. Emulsionbase Deionized water 29.78 Cetyl alcohol (1) 2.24 Stearyl alcohol (2)2.24 Ceteareth-25 (3) 1.50 Phenoxyethanol (4) 0.11 Sodium benzoate (5)0.09 Tetrasodium EDTA (87%) (6) 0.04 Ammonium hydroxide (13) 13.60

[0126] These products are made using the following protocols:

[0127] Peroxide Base:

[0128] The first stage is to make the emulsion base; this is prepared byadding to a vessel deionized water and commencing agitation, and thenheating to 82° C. Then tetrasodium EDTA and sodium benzoate are addedand dissolved, followed by addition of ceteareth25, cetyl alcohol andstearyl alcohol. During the addition process the temperature ismaintained above 80° C., finally phenoxyethanol is added, the mixture isthen homogenized for 30 min. The emulsion structure is obtained bycooling whilst still high shear mixing the product down below 50° C. Theemulsion base is then left to thicken for 60 min.

[0129] The chelants are added to the deionised water with mixing to formthe chelant premix. This is then added with stirring to the pre-madeemulsion base. Adding the peroxide mix water followed by hydrogenperoxide to the emulsion base/chelant premix and stirring untilhomogeneous makes the completed peroxide base.

[0130] Carrier Base for Dyes

[0131] The carrier base for dyes is prepared by adding water to a vesseland commencing agitation, followed by the addition of acetic acid, thenby the emulsion base (see emulsion base preparation describedhereinbefore for the peroxide base). When fully mixed, ammoniumhydroxide is added to the mixture and the stirring continued until theproduct is homogenous.

[0132] Equal weights of the two components, the peroxide base andcarrier base for dyes are mixed together thoroughly to produce thebleaching system. To each dry untreated hair switch, 4 g of thisbleaching system is then applied, and thoroughly worked into the hair,using the fingers, to ensure even, complete, coverage. The hair switchis then wrapped in cling film and incubated in an oven at 30° C. for 30minutes, after which the product is rinsed for 2 minutes (in a sinkfitted with a shower attachment set with a flow rate of 6±1 L min⁻¹ anda temperature of 37±2° C.) with finger agitation. Finally the switchesare dried using a hot air drier (Babyliss Lightweight Professional model1015 (1400 W) for 3 min. The bleached hair switches are then washed in asink fitted with a shower attachment set with a flow rate of 6±1 L min⁻¹and a temperature of 37±2° C. Switches are initially wetted under theshower attachment for 30s. The hair is then removed from the water flowand 0.2 g of shampoo (Pantene Pro-V Clarifying Shampoo) is applied downeach switch, and then lathered for 30 s by hand before rinsing for 60 sunder the shower. The hair is again removed from the shower, and has afurther 0.2 g of shampoo applied, and lathered for 30s before finallyrinsing under the shower for 60s. Hair switches are then dried using ahot air drier (Babyliss Lightweight Professional model 1015 (1400 W) for3 min. This washing protocol comprising two shampoo applications and onedrying step is defined as a single wash cycle. This washing method isthen repeated again through another complete wash cycle. The dry hairswitches are then bleached again according to the method outlined aboveand subsequently washed again through two complete wash cycles. Thishair is hereinafter defined as “damaged” hair and is hereafter used ahydrophilic hair substrate.

[0133] Hair Treatment

[0134] The functionalised silicone under investigation for durability isprepared for assessment using the following method. The functionalisedsilicone polymer is pre-mixed with the durability additive untilhomogeneous. To deliver the silicone/additive mixture, a matrixcomprising 36 wt. % of the “emulsion base”, described hereinbefore foruse in the preparation of the damaged hair substrate, obtained primarilythrough dilution with water, but also optionally comprising hydrogenperoxide and ammonium hydroxide, is used. Within the matrix, 1.75% ofthe silicone/additive under investigation is thoroughly dispersed usingconventional techniques. A sufficient amount of product is applied tofour chemically damaged hair switches for a sufficient time to providean initial deposition above 100 ppm. The hair is then rinsed to removethe matrix (in a sink fitted with a shower attachment set with a flowrate of 6±1 L min⁻¹ and a temperature of 37±2° C.) with fingeragitation. The switches are dried using a hot air drier (BabylissLightweight Professional model 1015 (1400 W) for 3 min.

[0135] When the switches are dry they are split into two groups bothcomprising equal numbers of damaged hair switches. The first are used tomeasure the initial deposition. The second set is washed to assess thesilicone durability. The hair switches are washed in a sink fitted witha shower attachment set with a flow rate of 6±1 L min⁻¹ and atemperature of 37±2° C. Switches are initially wetted under the showerattachment for 30 s. The hair is removed from the water flow and 0.2 gof shampoo (“Pantene Classic Clean Shampoo”) is applied along eachswitch, and then lathered for 30 s by hand before rinsing for 60 s underthe shower. The switch then has a further 0.2 g of shampoo application,and is lathered for 30 s before finally rinsing under the shower for 60s. Hair switches are then dried using a hot air drier (BabylissLightweight Professional model 1015 (1400 W) for 3 min. This protocolcomprising two shampoo applications and one drying step is defined asone complete wash cycle. This washing protocol is then repeated againthrough another eleven complete cycles (to make twelve wash cycles intotal). These switches are then measured for silicone deposition toassess the durability performance.

[0136] Silicone Deposition Measurement

[0137] A wavelength dispersive X-Ray Fluoresence spectrometer (PhillipsElectronics, PW2404 Sequential “4000W” X-Ray Spectrometer System) isutilised to determine the silicone deposition level on hair. Thespectrometer is fitted with a Rhodium tube and includes an InSb crystalto facilitate high sensitivity silicone detection.

[0138] Characteristic x-ray photons are produced from the ejection of aninner shell electron of an silicone atom followed by a transition of anelectron from a higher energy state to the empty inner shell. X-rayfluorescence of silicone in polydimethylsiloxane (PDMS) is directlyproportional to the amount of PDMS deposited on the hair. A criticalcomponent to facilitate the use of XRF technology is the ability topresent the sample to the spectrometer in a consistent manner. The hairswitch is arranged in a custom-made sample holder, which presents acontinuous, flat, aligned hair surface across the exposed sample area(16 mm diameter). The sample is analysed under a helium atmosphere usinga Tube voltage of 32 kV and current of 125 mA, with anirradiation/acquisition time of 60 s.

[0139] The drift in the analytical signal is regularly monitored andevaluated. The preferred approach employed is to use a known standardthat does not need to be prepared each time the drift is assessed. AnAusmon sample is an appropriate monitor sample for many applications,including silicon determinations. A drift correction with the Ausmonsample for silicon is performed at the beginning of each day samples areanalyzed. The calculated drift is below 3% between sets of analysis.

[0140] Calculation of the amount of silicone on hair in units of ppmfrom can be made with equation 1.

x ₂=(I−b ₁)/m ₁  (1)

[0141] Where m₁ and b₁ are calculated from a calibration curveconstructed from measurements of the XRF signal as a function of theamount of silicone deposited on hair subsequently assayed using atomicabsorption on the extracted silicone.

[0142] To translate the XRF silicone deposition data obtained ashereinbefore described into a measure of silicone durability, it isnecessary to generate a silicone durability index value. To generate thesilicone durability index value the following equation is employed:${{Silicone}\quad {durability}\quad {index}\quad {value}\quad (\%)} = {\frac{{Dep}\left( {12\quad {cycle}} \right)}{{Dep}({initial})} \times 100}$

[0143] Where Dep(initial) equals the XRF deposition value obtained onhair after silicone deposition with no washing cycles, Dep(12 cycles)equals the XRF deposition value obtained on hair after siliconedeposition and subsequent 12 wash cycles.

[0144] Viscoelasticity Measurement of the Functionalized Silicone Fluids

[0145] The AR 500 rotational Rheometer (TA Instruments) is used todetermine the G′ and G″ of the functional silicone fluids used herein.The determination is performed at 25° C., with the 6 cm acryllicparrellel plate measuring system set with a 100 micron gap and isperformed via the programmed application of a oscillatory stress of 2 Paover a oscillation frquency range of 1 to 40 Hz. This data is used todetermine the ratio of G′ to G″. A minimum of 30 data points is recordedover a linear frequency ramp. These data is used to determine the meanratio of G′ to G″ between 20 and 40 Hz.

EXAMPLES

[0146] The following examples further describe and demonstrate thepreferred embodiments within the scope of the present invention. Theexamples are given solely for the purpose of illustration, and are notto be construed as limitations of the present invention since manyvariations thereof are possible without departing from its scope.

Examples 1-2 Colorant Compositions

[0147] Peroxide base #1 #2 Ingredients Wt % Wt % Emulsion base:Deionized water 29.17 29.17 Cetyl alcohol (1) 2.20 2.20 Stearyl alcohol(2) 2.20 2.20 Ceteareth-25 (3) 1.47 1.47 Phenoxyethanol (4) 0.11 0.11Sodium benzoate (5) 0.09 0.09 Tetrasodium EDTA (87%) (6) 0.04 0.04Deionized water 32.00 32.00 Pentasodium pentetate (40%) (7) 0.24 0.24Hydroxyethane diphosphonic acid 0.16 0.16 (60%) (8) Phosphoric acid(75%) (9) 0.08 0.08 Sodium stannate (95%) (10) 0.04 0.04 Hydrogenperoxide (35%) (11) 16.80 16.80 Deionized water 10.40 10.40Functionalized Silicone premix: MQ resin sold under the name 0.025 0.005SR1000 by the company GE Bayer Silicones Aminopolyether functionalsilicone 4.995 B available from the Dow Corning UK under order numberJV. 0211.10 Aminofunctional silicone A 1.80 available from Dow CorningUK under order number JV.0208.13 Aminofunctional polydimethylsiloxanesold under the name DC 2-8566 silicone fluids by the company Dow corning

[0148] Carrier base for dye base #1 #2 Ingredients Wt % Wt % Deionizedwater 46.49 46.49 Acetic acid (50%) (12) 3.91 3.91 Emulsion base (seeingredients 36.00 36.00 above) Ammonium hydroxide (13) 13.60 13.60

[0149] Production of the Example Colorant Applications

[0150] Peroxide Base:

[0151] The emulsion base is prepared by adding to a vessel the deionizedwater and commencing agitation with heating to 82° C. Then thepreservatives (tetrasodium EDTA, sodium benzoate) are added anddissolved. This is followed by addition of ceteareth25, cetyl alcoholand stearyl alcohol while keeping the temperature above 80° C. Thenphenoxytol is added. The mixture is then fully blended hot through arecirculation line and homogenized. The emulsion structure is obtainedby cooling the product down below 50° C. and shearing while cooling. Theproduct is left to thicken for 60 min.

[0152] The chelant premix is prepared by adding the chelants to waterand mixing them together in a vessel. Then this solution is added to theemulsion base. The completed peroxide base is made by adding water tothe previous mixture followed by the hydrogen peroxide while stirring.

[0153] The functionalised silicone and organosiloxane resin arepre-mixed together under agitation and then added to the peroxide baseand and stirred until the desired particle size is obtained.

[0154] Carrier System for Dye Base:

[0155] The carrier base is prepared by adding water to a vessel andcommencing agitation, followed by the addition of acetic acid. Thenemulsion base (see emulsion base preparation described above) is added.When fully homogenized, ammonium hydroxide is added to the mixture.

[0156] For application to hair the peroxide base and the dye base aremixed together at a 1:1 ratio and applied to dry hair.

Examples 3-4 After Colorant Conditioners

[0157] #3 #4 Ingredients Wt % Wt % Deionized water 59.00-qs 59.00-qsEmulsion base: Deionized water 29.76 29.76 Cetyl alcohol (1) 2.25 2.25Stearyl alcohol (2) 2.25 2.25 Ceteareth-25 (3) 1.50 1.50 Phenoxyethanol(4) 0.11 0.11 Sodium benzoate (5) 0.09 0.09 Tetrasodium EDTA (87%) (6)0.04 0.04 Citric acid anhydrous fine (14) pH trim pH trim Siliconepremix: MQ resin sold under the name SR1000 by 0.025 0.005 the companyGE Bayer Silicones Aminopolyether functional silicone B 1.80 availablefrom DOW Corning, UK, under order number VJ.0211.10 Amino functionalsilicone A available from 4.975 DOW Corning, UK, under order numberVJ.0208.13

[0158] Composition Preparation

[0159] The conditioner composition is prepared by adding to a vessel thedeionized water and the emulsion base (see emulsion base preparationdescribed above) while stirring. When homogenized citric acid is addedto the mixture until the pH of the emusltion is between 5 and 6.

[0160] The functionalized silicones premix is prepared by pre-mixingtogether the functionalised silicone fluid and the organosiloxane resinwith agitation. The functionalised silicone premix is then added to themain mix and stirred until the desired particle size is obtained.

What is claimed is:
 1. A hair treatment composition comprising a mixture of (a) a functionalized silicone polymer having an interfacial tension of less than or equal to about 15 mN/m and a hydrophilicity index of less than about 100; and (b) a durability additive which is miscible with the functionalized silicone wherein the mixture has a (Tan δ)⁻¹ greater than zero.
 2. A hair treatment composition according to claim 1, wherein the interfacial tension is less than about 12 mN/m and the hydrophilicity index is less than or equal to about 99.5.
 3. A hair treatment composition according to claim 1, wherein the interfacial tension is less than about 8 mN/m.
 4. A hair treatment composition according to claim 1, wherein (Tan δ)⁻¹ is in the range from about 0.001 to less than or equal to about 0.1.
 5. A hair treatment composition according to claim 1, wherein the ratio of functionalized silicone to durability additive is in the range from about 5:1 to about 1000:1.
 6. A hair treatment composition according to claim 1, comprising from about 0.1 to about 20 wt % of the mixture.
 7. A hair treatment composition according to claim 1, which is in the form of an oil-in-water emulsion.
 8. A hair treatment composition according to claim 1, which is in the form of an oil-in-water emulsion and comprising 0.1% to about 15% based on the weight of the aqueous continuous phase of emulsifier.
 9. A hair treatment composition according to claim 8, wherein the emulsifier comprises one or more of an anionic surfactant, cationic surfactant, amphoteric surfactant, water-soluble polymeric surfactant, water soluble silicone-containing surfactant and a non-ionic surfactant.
 10. A hair treatment composition according to claim 8, wherein said emulsifier is a surfactant wherein the surfactant comprises C₁₆-C₂₂ fatty alcohols and/or fatty alcohol ethoxylates with about 1 to about 30 ethylene oxide groups.
 11. A hair treatment composition according to claim 8, wherein said emulsifier is a surfactant wherein the sufactant comprises a mixture of C₁₆₋₂₂ fatty alcohols and C₁₆₋₂₂ fatty alchol ethoxylates in a ratio of between about 10:1 to about 0.5:1.
 12. A hair treatment composition according to claim 1, wherein the functionalized silicone is an organomodified silicone of the pendant or graft type according to the following formula:

or a block copolymer type according to the following formula:

where Me is methyl, m is greater than or equal to 1, n is about 50 to about 2000, p is about 0 to about 50, q is about 0 to about 50, r is about 0 to about 50, s is about 0 to about 50, wherein p+q+r+s is greater than or equal to 1, B¹ is H, OH, an alkyl or an alkoxy group and organic groups A¹, A², A³ and A⁴ are straight, branched or mono- or polycyclic aliphatic, mono or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic or heteroolefinic moiety comprising about 3 to about 150 carbon atoms together with about 0-50 heteroatoms incorporating one or more polar substituents selected from electron withdrawing, electron neutral, or electron donating groups with Hammett sigma para values between about −1.0 and about +1.5.
 13. A hair treatment composition according to claim 12, wherein the polar substituents comprise groups (α¹, α², α³, and α⁴ as defined below; S-linked groups including Sα¹, SCN, SO₂α¹, SO₃α¹, SSα1¹, SOα¹, SO₂Nα¹α², SNα¹α², S(Nα¹) α², S(O)(Nα¹) α², Sα¹(Nα²), SONα¹α²; O-linked groups including Oα¹, OOα¹, OCN, ONα¹α²; N-linked groups including Nα¹α², Nα¹α²α³+, NC, Nα¹Oα²,Nα¹Sα², NCO, NCS, NO₂, N=Nα¹, N=NOα¹, Nα¹CN, N=C=Nα¹, Nα¹Nα²α³, Nα¹Nα²Nα³Nα⁴, Nα¹N=Nα²; COX, CON₃, CONα¹α², CONα¹COα², C(=Nα¹)Nα¹α², CHO, CHS, CN, NC, and X, where: α¹, α², α³, and α⁴ are straight, branched or mono or polycyclic aliphatic, mono or polyunsaturated alkyl, aryl, heteroalkyl, heteroaliphatic or heteroolefinic moiety comprising about 3 to about 150 carbon atoms together with about 0-50 heteroatoms incorporating one or more of 0, N, S, P, and X is F, Cl, Br, or I.
 14. A hair treatment composition according to claim 12, wherein the one or more polar substituents comprise oxygen, such that the oxygen contents of the summation of the one or more polar substituents is from about 1% to about 17% of the weight of the functionalized silicone and the silicone content is from about 45 to about 95% of the weight of the functionalized silicone.
 15. A hair treatment composition according to claims 12, wherein the functionalized silicone comprises polyoxyalkylene substituents.
 16. A hair treatment composition according to claim 12, wherein the functionalized silicones are according to the following formula:

where Me equals methyl; R¹ is methyl or R² or R³; R² is —(CH₂)_(a)—NH—[(CH₂)_(a)—NH]_(b)—H; and R³ is —(CH₂)_(a)—(OC₂H₄)_(m)—(OC₃H₆)_(n)—OZ; wherein x is about 50 to about 1500, y is about 1 to about 20, z is about 1 to about 20; a is about 2 to about 5, b is about 0 to 3, m is about 1 to about 30; n is about 1 to about 30, and Z is H, an alkyl group with about 1-4 carbons, or an acetyl group, with the proviso that when y is 0, R¹ is an R² group, and when z is 0, R¹ is an R³ group.
 17. A hair treatment composition according to claim 15, wherein the polyoxyalkylene content is from about 5 to about 42% and the silicone content is from 67 to about 95%.
 18. A hair treatment composition according to claim 1, comprising a functionalized silicone selected from:

e) mixtures thereof.
 19. A hair treatment composition according to claim 1, wherein the durability additive is an organosiloxane resin.
 20. A hair treatment composition according to claim 1, wherein the durability resin is an organosiloxane resin wherein the organosiloxane resins comprise combinations of R₃SiO_(1/2) “M” units, R₂SiO “D” units, RSiO_(3/2) “T” units, SiO₂ “Q” units in ratios to each other that satisfy the relationship R_(n)SiO_((4-n)/2) where n is a value between 1.0 and 1.50 and R is a methyl group.
 21. A hair treatment composition according to claim 20, wherein the resins comprise repeating monofunctional R₃SiO_(1/2) “M” units and quadrafunctional SiO₂ “Q” units.
 22. A hair treatment composition according to claim 21, wherein the ratio of the “M” to “Q” functional units is from about 0.7 and the value of n is about 1.2.
 23. A hair treatment composition according to claim 19, wherein the organosiloxane resins are solid at about 25° C. and have a molecular weight range of from about 1,000 to about 10,000 grams/mole.
 24. A Hair treatment composition according to claim 1, additionally comprising a hair bleaching component and/or a hair dyeing component.
 25. Hair treatment kit comprising: (c) an oxidative bleaching composition (d) a dye composition; and  a hair treatment composition according to claim 1 comprised within component (a) and/or within component (b) and/or is provided as a separate component. 